15/9/2014

Liquid Fuels
Petroleum

Origin of Petroleum
Petroleum crude oil, or simply crude oil, is a naturally
occurring, flammable and usually dark brown or
greenish colored liquid found primarily in underground
geological formations.

According to the modern theory:

Petroleum is formed by decay and decomposition of
marine animals and plants.
Due to some upheavals and earthquakes, the forests
and animals got buried inside earth crust.
Due to high temperature and pressure in the earth for
ages, biological matter decomposed into petroleum.

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Difference between origins of Oil and Coal

Coal was formed mainly from land plants decaying under
mildly reducing conditions.
Petroleum oil from sea plants and animals decay under
strongly reducing conditions.
Coal seams remain static where formed.
Oil can migrate under effects of temperature and pressure.

Production of Petroleum
Petroleum almost always occurs
along with gas called natural gas.
When the oil well contains both oil
and gas it is called wet well.
If well contains only gas it is called
as dry well.

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Production of Petroleum
Three conditions must be present for oil reservoirs to form
1. A source rich in hydrocarbon material buried deep enough.
2. A porous and permeable reservoir rock for it to accumulate in.
3. A cap rock (seal) or other mechanism that prevents it from
escaping to the surface.
Within these reservoirs, fluids will typically organize themselves
like a three-layer cake with a layer of water below the oil layer and
a layer of gas above it, although the different layers vary in size
between reservoirs.

Production of Petroleum
Petroleum was not originally formed in the pools where it is found
today.
Crude petroleum deposits were formed near seashores.
Ac on of water shi in loca on of oil pool.
The oil kept on moving until it became trapped in hard rocks.
This makes it impossible for the gas or oil to escape and the water
keeps the pool of oil under pressure.

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Production of Petroleum
Wells are drilled into oil reservoirs to extract the
crude oil.
Primary Production Methods
Natural lift -- natural reservoir pressure force
the oil to the surface.
Usually sufficient for a while after reservoirs are
first tapped.
10 percent of a reservoir's original-oil-in-place
(referred to as "OOIP") is typically produced
during primary recovery
In some reservoirs, such as in the Middle East,
the natural pressure is sufficient over a long time.

Production of Petroleum
Secondary Production Methods
In order to extend the productive life of an oil field, most oil
producers have used secondary recovery methods.
These methods generally involve injecting water into the
underground reservoir.
Water displaces the oil and drive it into the wellbore where it can be
lifted to the surface by pumps.
Natural gas (often produced simultaneously with the oil) is re-
injected to maintain reservoir pressure, thus driving the oil into the
wellbore.
These methods generally raise the overall oil recovery to 20 40
percent of the original-oil-in-place.

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Production of Petroleum
Tertiary Production Methods
Even after secondary stage, 60-80% oil still remains in
the reservoirs.
Using tertiary methods, 30 60 %, or more of the
reservoirs OOIP can be recovered completely.
This is achieved by using steam injection to raise the
temperature of the oil, which reduces the oil's
viscosity and enhanced flow through the reservoir.
or
Raising the pressure within the reservoir by the
injection of a gas such as N2 or CO2 that expand in the
reservoir and push the additional oil to the wellbore.

Composition of Crude Oil

Crude oil consists mostly of hydrocarbons with
small amounts of other chemical compounds that
may contain N, O or S.
It may also contain trace amounts of heavy
metals such as Fe, Ni, Cu and V.

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Pre-Treatment of an Oil at an Oil Field

Oil and gas when they come out of oil field are
separated.
Crude oilas it comes out of well contains
H2O---25% and salts (MgCl2, CaCl2 etc), up to 2000-5000
mg/L.
Water in crude requires extra heat for its distillation
and increases its cost of transportation.
Salt in crude oil causes corrosion during its processing.
These can be separated mechanically by utilizing
mechanical method of separation.
In this separation method, crude oil is subjected to
centrifuging, filtration and settling after heating to 120-
160C at 6-8atm pressure.

Refining of Petroleum
Crude oil is a complex mixture of mainly hydrocarbon compound
molecules.
A mixture consists of two or more elements or compounds which
are not chemically combined.
Crude oil can be separated by physical methods, e.g. by fractional
distillation, as different fractions in oil have different boiling points.

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Fractional Distillation
Distillation is the process of separating two or more
liquids based on differences in their boiling points.
Pre-treated crude oil is heated in pipes in the furnace
to a temperature of about 400C.

Fractional Distillation
The vapors of petroleum are fed
into the fractionating column
from the bottom.
As the vapors enter the column,
they rise up and gradually get
cooled.
At the bottom of the furnace, the
temperature is about 400oC. Here,
the component that has a boiling
point close to 400oC condenses
(liquifies) first and collects on the
tray.
From the tray it is let off through
the outlet pipe.

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The remaining vapors rise up through the bubble caps.

When the vapors reach a particular height in the tower, the fraction that
has a boiling point close to the temperature at that height condenses on
the tray.
The remaining vapors continue to rise upwards.
Like this, at different levels in the tower, different fractions get condensed,
collect on the trays and flow out of the outlet pipes.
D Refinery Gas (LPG) mainly propane and butane
I
S Gasoline or Petrol ( 30-200C)
T Kerosene Oil ( 140-290C)
I
L Diesel Oil ( 140-300C)
L Lubricating Oil (200-350C)
A
T Light Fuel Oil (200C)
I Heavy Fuel Oil (250C)
O Road making bitumen or tar
N
Wax

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Typical Products Yields in Crude Distillation

The yield of products of a typical crude
distillation is given below:
Petrol 18% Gas Oil 12%

Naphtha 6% Lubricating Oil 12%

Kerosene 10% Wax 9%

Diesel 8% Residue Pitch 25%

Liquid Fuels
Usage
Used extensively in industrial applications

Some important liquid fuels include

Furnace oil
Light diesel oil
Motor Spirit
Petrol
Kerosene
Ethanol
LSHS (low sulfur heavy stock)

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Properties of Fuel Oils

Some important properties of
liquid fuels include:
Flash Point
Fire Point
Viscosity
Specific Gravity
Cloud Point
Pour Point
Calorific Value
Specific Heat
Sulfur Content
Ash Content

Flash Point
It is the minimum temperature at which a fuel
oil gives out sufficient vapors to form an
inflammable mixture with air.
The fuel oil catches fire momentarily when
flame is applied.
At the flash point, the vapor may cease to
burn when the source of ignition is removed.
It is an indication of how easily a fuel may
burn.

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Why to measure Flash Point?

Flash point gives idea about:
Amount of low boiling fraction present in the liquid fuel.
Explosion hazards.
Volatility of the liquid fuels.
Materials with higher flash points are less flammable or hazardous than
chemicals with lower flash points.
Hazard Flash Point
Flash point > 200oF
Very Low Hazard
(93oC)
Flash point 150oF to 200oF
Moderate Low Hazard
(66oC to 93oC)

Flash point 100oF to 150oF

High to Moderate Hazard
(38oC to 66oC)
Flash point 0oF to 100oF
Extreme to High Hazard
(-18oC to 38oC)
Flash point < 0oF
Extreme Hazard
(-18oC)

Fire Point
It is the lowest temperature at which vapors
given off by the fuel oil ignites and continues to
burn for at least 5 seconds.
At the flash point, a lower temperature, a
substance will ignite briefly, but vapor might not
be produced at a rate to sustain the fire.
It is an indication of how easily a fuel may burn.
In most cases, fire point is 5-10 C higher than
flash point.
Usually both the temperatures are measured.

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Ignition Temperature
The ignition temperature is the minimum temperature at
which the fuel ignites (catches fire) in an oxidizing
atmosphere without any external source of fire.
The term ignition temperature is also used to describe
the temperature of a hot surface that would cause
flammable vapors to ignite.

Pensky Martens--Flash Point Apparatus

Four Openings in the lid
1. For thermometer
2. For Stirrer
3. For test flame
4. For air admission

1. Oil is heated by the burner.

2. Exposed to flame after every 1 C
rise in temperature.
3. Heating rate 5 C/min. Oil Cup:
4. Stirrer Rotation1 to 2 RPM. 5cm dia, 5.5 cm height
5. Appearance of flash --- Flash point

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Cloud Point
When an oil is cooled at a specified rate, the temperature at which
it becomes cloudy or hazy is called the cloud point of oil.

Haziness may be due to separation of wax or increase of viscosity

at low temperature.

The presence of solidified waxes thickens the oil and clogs fuel
filters and injectors in engines.

Therefore, cloud point indicates the tendency of the oil to plug

filters or small orifices at cold operating temperatures.

Pour Point
The temperature at which an oil just ceases to flow is
called pour point.

It determines the temperature below which an oil

cannot be used as a lubricant.

Cloud and Pour Point indicates the suitability of

lubricants in cold condition.

The difference of pour point and cloud point is

usually 4-6F.

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Cloud and Pour Point Apparatus

1. Flat bottom test tube is

half filled with oil.
2. Thermometer in oil.
3. Oil is cooled
continuously and
slowly.
4. After every degree fall
of temperature, tube is
withdrawn.
Cooling continues and test tube is withdrawn after every
5. The temperature at
3C fall of temperature
which cloudness is
Tilted to observe the flow or pour of the oil.
noticed is recorded at
The temperature at which it does not flow even when kept
the cloud point.
horizontal for 5 seconds is taken as the pour point.

Viscosity
Ability of the liquid to resist its flow, when
subjected to some force e.g shear or tensile.
A liquid is said to be less viscous if it flows easily.
A fixed volume of liquid at a fixed
temperature is allowed to flow through
the standard capillary tube and the time
of flow is noted.
Dimensions of Oil Cup:
Diameter: 46.5 mm
Height: 90 mm
Bore diameter and length: 1.62 and
10mm respectively.
Jet can be opened and closed by a valve
rod.
Viscosity, measured in redwood seconds
via this method, can be converted into
centistokes using mathematical relations..

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